Pesticidal Mixtures

ABSTRACT

The present invention relates Fungicidal mixtures comprising, as active components, 1) 4-[[6-[2-(2,4-difluorophenyl) -1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile as compound I and 2) 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one as compound II and methods to combat phytopathogenic fungi based on such mixtures.

The present invention relates to fungicidal mixtures comprising asactive components,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrileas compound I and1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one as compound II.

Moreover, the invention relates to an use of the mixture for controllingphytopathogenic harmful fungi and to a method for controllingphytopathogenic pests, wherein the pest, their habitat, breedinggrounds, their locus or the plants to be protected against pest attack,the soil or plant propagation material are treated with an effectiveamount of the mixture.

The term “plant propagation material” is to be understood to denote allthe generative parts of the plant such as seeds and vegetative plantmaterial such as cuttings and tubers (e. g. potatoes), which can be usedfor the multiplication of the plant. This includes seeds, roots, fruits,tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants,including seedlings and young plants, which are to be transplanted aftergermination or after emergence from soil. These young plants may also beprotected before transplantation by a total or partial treatment byimmersion or pouring. In a particular preferred embodiment, the termpropagation material denotes seeds.

Compound I and analogues as well as their pesticidal action and methodsfor producing them and mixtures are known e.g. from WO 2016187201,WO2018098216, WO2018098243, WO2018098245.

Compounds II as well as their pesticidal action and methods forproducing them are generally known (cf.:http://www.alanwood.net/pesticides/); these substances are commerciallyavailable. The compounds described by IUPAC nomenclature, theirpreparation and their pesticidal activity are also known (WO 2013162072).

One typical problem arising in the field of pest control lies in theneed to reduce the dosage rates of the active ingredient in order toreduce or avoid unfavorable environmental or toxicological effectswhilst still allowing effective pest control.

In regard to the present invention the term pests embrace harmful fungiand animal pests.

Another problem encountered concerns the need to have available pestcontrol agents which are effective against a broad spectrum of harmfulfungi and harmful animal pests.

There also exists the need for pest control agents that combineknock-down activity with prolonged control, that is, fast action withlong lasting action.

Another difficulty in relation to the use of pesticides is that therepeated and exclusive application of an individual pesticidal compoundleads in many cases to a rapid selection of pests, that means animalpests, and harmful fungi, which have developed natural or adaptedresistance against the active compound in question. Therefore, there isa need for pest control agents that help prevent or overcome resistance.

Another problem underlying the present invention is the desire forcompositions that improve plants, a process which is commonly andhereinafter referred to as “plant health”.

The term plant health comprises various sorts of improvements of plantsthat are not connected to the control of pests. For example,advantageous properties that may be mentioned are improved cropcharacteristics including: emergence, crop yields, protein content, oilcontent, starch content, more developed root system (improved rootgrowth), improved stress tolerance (e.g. against drought, heat, salt,UV, water, cold), reduced ethylene (reduced production and/or inhibitionof reception), tillering increase, increase in plant height, bigger leafblade, less dead basal leaves, stronger tillers, greener leaf color,pigment content, photosynthetic activity, less input needed (such asfertilizers or water), less seeds needed, more productive tillers,earlier flowering, early grain maturity, less plant verse (lodging),increased shoot growth, enhanced plant vigor, increased plant stand andearly and better germination; or any other advantages familiar to aperson skilled in the art.

It was therefore an object of the present invention to providepesticidal mixtures which solve the problems of reducing the dosage rateand/or enhancing the spectrum of activity and/or combining knock-downactivity with prolonged control and/or to resistance management and/orpromoting the health of plants.

We have found that this object is in part or in whole achieved by thefungicidal mixtures comprising as active components comprising as activecomponents,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrileas compound I and1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-oneas compound II.

Especially, it has been found that the mixtures as defined in the outsetshow markedly enhanced action against pests compared to the controlrates that are possible with the individual compounds and/or is suitablefor improving the health of plants when applied to plants, parts ofplants, seeds, or at their locus of growth.

It has been found that the action of the inventive mixtures comprisingcompound I and compound II goes far beyond the fungicidal and/or planthealth improving action of the active compounds present in the mixturealone (synergistic action).

Moreover, we have found that simultaneous, that is joint or separate,application of the compound I and the compound II or successiveapplication of the compound I and the compound II allows enhancedcontrol of harmful fungi, compared to the control rates that arepossible with the individual compounds (synergistic mixtures).

Moreover, we have found that simultaneous, that is joint or separate,application of the compound I and the compound II or successiveapplication of the compound I and the compound II provides enhancedplant health effects compared to the plant health effects that arepossible with the individual compounds.

The ratio by weight of compound I and compound II in binary mixtures isfrom 10000:1 to 1:10000, from 500:1 to 1:500, preferably from 100:1 to1:100 more preferably from 50:1 to 1:50, most preferably from 20:1 to1:20, including also ratios from 10:1 to 1:10, 1:5 to 5:1, or 1:1.

All above-referred mixtures are herein below referred to as “inventivemixtures”.

The inventive mixtures can further contain one or more insecticides,fungicides, herbicides.

The inventive mixtures can be converted into customary types ofagrochemical compositions, e. g. solutions, emulsions, suspensions,dusts, powders, pastes, granules, pressings, capsules, and mixturesthereof. Examples for composition types are suspensions (e.g. SC, OD,FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES,ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders ordusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules(e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as wellas gel formulations for the treatment of plant propagation materialssuch as seeds (e.g. GF). These and further compositions types aredefined in the “Catalogue of pesticide formulation types andinternational coding system”, Technical Monograph No. 2, 6^(th) Ed. May2008, CropLife International.

The compositions are prepared in a known manner, such as described byMollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001;or Knowles, New developments in crop protection product formulation,Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers orfillers, surfactants, dispersants, emulsifiers, wetters, adjuvants,solubilizers, penetration enhancers, protective colloids, adhesionagents, thickeners, humectants, repellents, attractants, feedingstimulants, compatibilizers, bactericides, anti-freezing agents,anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents,such as mineral oil fractions of medium to high boiling point, e.g.kerosene, diesel oil; oils of vegetable or animal origin;

aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol,propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones,e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acidesters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides,e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixturesthereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates,silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite,diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate,magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers,e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas;products of vegetable origin, e.g. cereal meal, tree bark meal, woodmeal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic,cationic, nonionic and amphoteric surfactants, block polymers,polyelectrolytes, and mixtures thereof. Such surfactants can be used asemulsifier, dispersant, solubilizer, wetter, penetration enhancer,protective colloid, or adjuvant. Examples of surfactants are listed inMcCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon'sDirectories, Glen Rock, USA, 2008 (International Ed. or North AmericanEd.)

Suitable anionic surfactants are alkali, alkaline earth or ammoniumsalts of sulfonates, sulfates, phosphates, carboxylates, and mixturesthereof. Examples of sulfonates are alkylarylsulfonates,diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates,sulfonates of fatty acids and oils, sulfonates of ethoxylatedalkylphenols, sulfonates of alkoxylated arylphenols, sulfonates ofcondensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes,sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates orsulfosuccinamates. Examples of sulfates are sulfates of fatty acids andoils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols,or of fatty acid esters. Examples of phosphates are phosphate esters.Examples of carboxylates are alkyl carboxylates, and carboxylatedalcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acidamides, amine oxides, esters, sugar-based surfactants, polymericsurfactants, and mixtures thereof. Examples of alkoxylates are compoundssuch as alcohols, alkylphenols, amines, amides, arylphenols, fatty acidsor fatty acid esters which have been alkoxylated with 1 to 50equivalents. Ethylene oxide and/or propylene oxide may be employed forthe alkoxylation, preferably ethylene oxide. Examples of N-substitutedfatty acid amides are fatty acid glucamides or fatty acid alkanolamides.Examples of esters are fatty acid esters, glycerol esters ormonoglycerides. Examples of sugar-based surfactants are sorbitans,ethoxylated sorbitans, sucrose and glucose esters oralkylpolyglucosides. Examples of polymeric surfactants are home- orcopolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for examplequaternary ammonium compounds with one or two hydrophobic groups, orsalts of long-chain primary amines. Suitable amphoteric surfactants arealkylbetains and imidazolines. Suitable block polymers are blockpolymers of the A-B or A-B-A type comprising blocks of polyethyleneoxide and polypropylene oxide, or of the A-B-C type comprising alkanol,polyethylene oxide and polypropylene oxide. Suitable polyelectrolytesare polyacids or polybases. Examples of polyacids are alkali salts ofpolyacrylic acid or polyacid comb polymers. Examples of polybases arepolyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even nopesticidal activity themselves, and which improve the biologicalperformance of the inventive mixtures on the target. Examples aresurfactants, mineral or vegetable oils, and other auxiliaries. Furtherexamples are listed by Knowles, Adjuvants and additives, Agrow ReportsDS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum,carboxymethylcellulose), inorganic clays (organically modified orunmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives suchas alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol,urea and glycerin. Suitable anti-foaming agents are silicones, longchain alcohols, and salts of fatty acids. Suitable colorants (e.g. inred, blue, or green) are pigments of low water solubility andwater-soluble dyes. Examples are inorganic colorants (e.g. iron oxide,titan oxide, iron hexacyanoferrate) and organic colorants (e.g.alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons,polyvinylacetates, polyvinyl alcohols, polyacrylates, biological orsynthetic waxes, and cellulose ethers.

Examples for composition types and their preparation are:

i) Water-Soluble Concentrates (SL, LS)

10-60 wt % of an inventive mixture and 5-15 wt % wetting agent (e.g.alcohol alkoxylates) are dissolved in water and/or in a water-solublesolvent (e.g. alcohols) ad 100 wt %. The active substance dissolves upondilution with water.

ii) Dispersible Concentrates (DC)

5-25 wt % of an inventive mixture and 1-10 wt % dispersant (e. g.polyvinylpyrrolidone) are dissolved in organic solvent (e.g.cyclohexanone) ad 100 wt %. Dilution with water gives a dispersion.

iii) Emulsifiable Concentrates (EC)

15-70 wt % of an inventive mixture and 5-10 wt % emulsifiers (e.g.calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolvedin water-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion.

iv) Emulsions (EW, EO, ES)

5-40 wt % of an inventive mixture and 1-10 wt % emulsifiers (e.g.calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolvedin 20-40 wt % water-insoluble organic solvent (e.g. aromatichydrocarbon). This mixture is introduced into water ad 100 wt % by meansof an emulsifying machine and made into a homogeneous emulsion. Dilutionwith water gives an emulsion.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt % of an inventive mixture arecomminuted with addition of 2-10 wt % dispersants and wetting agents(e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt %thickener (e.g. xanthan gum) and water ad 100 wt % to give a fine activesubstance suspension. Dilution with water gives a stable suspension ofthe active substance. For FS type composition up to 40 wt % binder (e.g.polyvinylalcohol) is added.

vi) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50-80 wt % of an inventive mixture are ground finely with addition ofdispersants and wetting agents (e.g. sodium lignosulfonate and alcoholethoxylate) ad 100 wt % and prepared as water-dispersible orwater-soluble granules by means of technical appliances (e. g.extrusion, spray tower, fluidized bed). Dilution with water gives astable dispersion or solution of the active substance.

vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)

50-80 wt % of an inventive mixture are ground in a rotor-stator millwith addition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3wt % wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g.silica gel) ad 100 wt %. Dilution with water gives a stable dispersionor solution of the active substance.

viii) Gel (GW, GF)

In an agitated ball mill, 5-25 wt % of an inventive mixture arecomminuted with addition of 3-10 wt % dispersants (e.g. sodiumlignosulfonate), 1-5 wt % thickener (e.g. carboxymethylcellulose) andwater ad 100 wt % to give a fine suspension of the active substance.Dilution with water gives a stable suspension of the active substance.

ix) Microemulsion (ME)

5-20 wt % of an inventive mixture are added to 5-30 wt % organic solventblend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt %surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate),and water ad 100%. This mixture is stirred for 1 h to producespontaneously a thermodynamically stable microemulsion.

x) Microcapsules (CS)

An oil phase comprising 5-50 wt % of an inventive mixture, 0-40 wt %water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt %acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- ortriacrylate) are dispersed into an aqueous solution of a protectivecolloid (e.g. polyvinyl alcohol). Radical polymerization initiated by aradical initiator results in the formation of poly(meth)acrylatemicrocapsules. Alternatively, an oil phase comprising 5-50 wt % of aninventive mixture according to the invention, 0-40 wt % water insolubleorganic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer(e.g. diphenylmethene-4,4′-diisocyanatae) are dispersed into an aqueoussolution of a protective colloid (e.g. polyvinyl alcohol). The additionof a polyamine (e.g. hexamethylenediamine) results in the formation ofpolyurea microcapsules. The monomers amount to 1-10 wt %. The wt %relate to the total CS composition.

xi) Dustable Powders (DP, DS)

1-10 wt % of an inventive mixture are ground finely and mixed intimatelywith solid carrier (e.g. finely divided kaolin) ad 100 wt %.

xii) Granules (GR, FG)

0.5-30 wt % of an inventive mixture is ground finely and associated withsolid carrier (e.g. silicate) ad 100 wt %. Granulation is achieved byextrusion, spray-drying or fluidized bed.

xiii) Ultra-Low Volume Liquids (UL)

1-50 wt % of an inventive mixture are dissolved in organic solvent (e.g.aromatic hydrocarbon) ad 100 wt %.

The compositions types i) to xiii) may optionally comprise furtherauxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezingagents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.

The resulting agrochemical compositions generally comprise between 0.01and 95%, preferably between 0.1 and 90%, and in particular between 0.5and 75%, by weight of active substance. The active substances areemployed in a purity of from 90% to 100%, preferably from 95% to 100%(according to NMR spectrum).

Solutions for seed treatment (LS), Suspoemulsions (SE), flowableconcentrates (FS), powders for dry treatment (DS), water-dispersiblepowders for slurry treatment (WS), water-soluble powders (SS), emulsions(ES), emulsifiable concentrates (EC) and gels (GF) are usually employedfor the purposes of treatment of plant propagation materials,particularly seeds. The compositions in question give, aftertwo-to-tenfold dilution, active substance concentrations of from 0.01 to60% by weight, preferably from 0.1 to 40%, in the ready-to-usepreparations. Application can be carried out before or during sowing.Methods for applying the inventive mixtures and compositions thereof,respectively, on to plant propagation material, especially seeds includedressing, coating, pelleting, dusting, soaking and in-furrow applicationmethods of the propagation material. Preferably, the inventive mixturesor the compositions thereof, respectively, are applied on to the plantpropagation material by a method such that germination is not induced,e. g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substancesapplied are, depending on the kind of effect desired, from 0.001 to 2 kgper ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.01to 1.0 kg per ha, and in particular from 0.05 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. bydusting, coating or drenching seed, amounts of active substance of from0.01-10kg, preferably from 0.1-1000 g, more preferably from 1-100 g per100 kilogram of plant propagation material (preferably seeds) aregenerally required.

When used in the protection of materials or stored products, the amountof active substance applied depends on the kind of application area andon the desired effect. Amounts customarily applied in the protection ofmaterials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of activesubstance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, ormicronutrients, and further pesticides (e.g. herbicides, insecticides,fungicides, growth regulators, safeners) may be added to the activesubstances or the compositions comprising them as premix or, ifappropriate not until immediately prior to use (tank mix). These agentscan be admixed with the compositions according to the invention in aweight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually froma predosage device, a knapsack sprayer, a spray tank, a spray plane, oran irrigation system. Usually, the agrochemical composition is made upwith water, buffer, and/or further auxiliaries to the desiredapplication concentration and the ready-to-use spray liquor or theagrochemical composition according to the invention is thus obtained.Usually, 20 to 2000 liters, preferably 50 to 400 liters, of theready-to-use spray liquor are applied per hectare of agricultural usefularea.

According to one embodiment, individual components of the compositionaccording to the invention such as parts of a kit or parts of a binarymixture may be mixed by the user himself in a spray tank or any otherkind of vessel used for applications (e. g. seed treater drums, seedpelleting machinery, knapsack sprayer) and further auxiliaries may beadded, if appropriate.

Consequently, one embodiment of the invention is a kit for preparing ausable pesticidal composition, the kit comprising a) a compositioncomprising component 1) as defined herein and at least one auxiliary;and b) a composition comprising component 2) as defined herein and atleast one auxiliary; and optionally c) a composition comprising at leastone auxiliary and optionally a further active component 3) as definedherein.

As said above, the present invention comprises an use of the mixture forcontrolling phytopathogenic harmful fungi and to a method forcontrolling phytopathogenic pests, wherein the pest, their habitat,breeding grounds, their locus or the plants to be protected against pestattack, the soil or plant propagation material are treated with aneffective amount of the mixture.

Advantageously, the inventive mixtures are suitable for controlling thefollowing fungal plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida)and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leafspot) on vegetables (e.g. A. dauci or A. porri), oilseed rape (A.brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A.grandis), rice, soybeans, potatoes and tomatoes (e. g. A. solani, A.grandis or A. alternata), tomatoes (e. g. A. solani or A. alternata) andwheat (e.g. A. triticina); Aphanomyces spp. on sugar beets andvegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici(anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (syn.Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph:Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northernleaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) oncereals and e. g. B. oryzae on rice and turfs; Blumeria (formerlyErysiphe) graminis (powdery mildew) on cereals (e. g. on wheat orbarley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: greymold) on fruits and berries (e. g. strawberries), vegetables (e. g.lettuce, carrots, celery and cabbages); B. squamosa or B. allii on onionfamily), oilseed rape, ornamentals (e.g. B eliptica), vines, forestryplants and wheat; Bremia lactucae (downy mildew) on lettuce;Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved treesand evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercosporaspp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C.zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane,vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice;Cladobotryum (syn. Dactylium) spp. (e.g. C. mycophilum (formerlyDactylium dendroides, teleomorph: Nectria albertinii, Nectria rosellasyn. Hypomyces rosellus) on mushrooms; Cladosporium spp. on tomatoes (e.g. C. fulvum leaf mold) and cereals, e. g. C. herbarum (black ear) onwheat; Claviceps purpurea (ergot) on cereals; Cochliobolus(anamorph:Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum),cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C.miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph:Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e.g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g.C. coccodes black dot), beans (e. g. C. lindemuthianum), soybeans (e. g.C. truncatum or C. gloeosporioides), vegetables (e.g. C. lagenarium orC. capsici), fruits (e.g. C. acutatum), coffee (e.g. C. coffeanum or C.kahawae) and C. gloeosporioides on various crops; Corticium spp., e. g.C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots)on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum onolive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vinedecline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines(e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black FootDisease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix(root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum(damping off) on soybeans; Drechslera (syn. Helminthosporium,teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D.teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), riceand turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia(syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora(formerly Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilumand/or Botryosphaeria obtuse; Elsinoe spp. on pome fruits (E. pyri),soft fruits (E. veneta: anthracnose) and vines (E. ampelina:anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (blackmold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E.betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E.cichoracearum), cabbages, oilseed rape (e. g. E. cruciferarum); Eu-typalata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn.Libertella blepharis) on fruit trees, vines and ornamental woods;Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum);Fusarium (teleomorph: Giabberella) spp. (wilt, root or stem rot) onvarious plants, such as F. graminearum or F. culmorum (root rot, scab orhead blight) on cereals (e. g. wheat or barley), F. oxysporum ontomatoes, F. solani (f. sp. glycines now syn. F. virguliforme) and F.tucumaniae and F. brasiliense each causing sudden death syndrome onsoybeans, and F. verticillioides on corn; Gaeumannomyces graminis(take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp.on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanaedisease); Glomerella cingulata on vines, pome fruits and other plantsand G. gossypii on cotton; Grainstaining complex on rice; Guignardiabidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plantsand junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp.(syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals, potatoesand rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) oncoffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines;Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeansand cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) oncereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew)on soybeans; Monoilinia spp., e. g. M. laxa, M. fructicola and M.fructigena (syn. Monilia spp.: bloom and twig blight, brown rot) onstone fruits and other rosaceous plants; Mycosphaerella spp. on cereals,bananas, soft fruits and ground nuts, such as e. g. M. graminicola(anamorph: Zymoseptoria tritici formerly Septoria tritici: Septoriablotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis: blackSigatoka disease) and M. musicola on bananas, M. arachidicola (syn. M.arachidis or Cercospora arachidis), M. berkeleyi on peanuts, M. pisi onpeas and M. brassiciola on brassicas; Peronospora spp. (downy mildew) oncabbage (e. g. P. brassicae), oilseed rape (e. g. P. parasitica), onions(e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P.manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) onsoybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P.tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam(syn. Leptosphaeria biglobosa and L. maculans: root and stem rot) onoilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off)on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn;Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leafspot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthephaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp.(wilt, root, leaf, fruit and stem root) on various plants, such aspaprika and cucurbits (e. g. P. capsid), soybeans (e. g. P. megasperma,syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight)and broad-leaved trees (e. g. P. ramorum: sudden oak death);Plasmodiophora brassicae (club root) on cabbage, oilseed rape, radishand other plants; Plasmopara spp., e. g. P. viticola (grapevine downymildew) on vines and P. halstedii on sun-flowers; Podosphaera spp.(powdery mildew) on rosaceous plants, hop, pome and soft fruits (e. g.P. leucotricha on apples) and curcurbits (P. xanthii); Polymyxa spp., e.g. on cereals, such as barley and wheat (P. graminis) and sugar beets(P. betae) and thereby transmitted viral diseases; Pseudocercosporellaherpotrichoides (syn. Oculimacula yallundae, O. acuformis: eye-spot,teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley;Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis oncucurbits or P. humili on hop; Pseudopezicula tracheiphila (red firedisease or, rotbrenner', anamorph: Phialophora) on vines; Puccinia spp.(rusts) on various plants, e. g. P. triticina (brown or leaf rust), P.striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis(stem or black rust) or P. recondita (brown or leaf rust) on cereals,such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugarcane and P. asparagi on asparagus; Pyrenopeziza spp., e.g. P. brassicaeon oilseed rape; Pyrenophora (anamorph: Drechslera) tritici-repentis(tan spot) on wheat or P. teres (net blotch) on barley; Pyriculariaspp., e. g. P. oryzae (teleomorph: Magnaporthe grisea: rice blast) onrice and P. grisea on turf and cereals; Pythium spp. (damping-off) onturf, rice, corn, wheat, cotton, oilseed rape, sunflowers, soybeans,sugar beets, vegetables and various other plants (e. g. P. ultimum or P.aphanidermatum) and P. oligandrum on mushrooms; Ramularia spp., e. g. R.collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barleyand R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice,potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetablesand various other plants, e. g. R. solani (root and stem rot) onsoybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctoniaspring blight) on wheat or barley; Rhizopus stolonifer (black mold, softrot) on strawberries, carrots, cabbage, vines and tomatoes;Rhynchosporium secalis and R. commune (scald) on barley, rye andtriticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice;Sclerotinia spp. (stem rot or white mold) on vegetables (S. minor and S.sclerotiorum) and field crops, such as oilseed rape, sunflowers (e. g.S. sclerotiorum) and soybeans, S. rolfsii (syn. Athelia rolfsii) onsoybeans, peanut, vegetables, corn, cereals and ornamentals; Septoriaspp. on various plants, e. g. S. glycines (brown spot) on soybeans, S.tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S.(syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula(syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) onvines; Setosphaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn.Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn,(e. g. S. reiliana, syn. Ustilago reiliana: head smut), sorghum andsugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthii: powderymildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoesand thereby transmitted viral diseases; Stagonospora spp. on cereals, e.g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn.Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat; Synchytriumendobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T.deformans (leaf curl disease) on peaches and T. pruni (plum pocket) onplums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits,vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalaraelegans); Tilletia spp. (common bunt or stinking smut) on cereals, suchas e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa(dwarf bunt) on wheat; Trichoderma harzianum on mushrooms, Typhulaincarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U.occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such asbeans (e. g. U. appendiculatus, syn. U. phaseoli), sugar beets (e. g. U.betae or U. beticola) and on pulses (e.g. U. vignae, U. pisi, U.viciae-fabae and U. fabae); Ustilago spp. (loose smut) on cereals (e. g.U. nuda and U. avaenae), corn (e. g. U. maydis corn smut) and sugarcane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears;and Verticillium spp. (wilt) on various plants, such as fruits andornamentals, vines, soft fruits, vegetables and field crops, e. g. V.longisporum on oilseed rape, V. dahliae on strawberries, oilseed rape,potatoes and tomatoes, and V. fungicola on mushrooms; Zymoseptoriatritici on cereals; Phaeosphaena maydis and Puccinia polysora.

Mixtures according to the invention are suitable for combatingphytopathogenic fungi, for example on cereals, such fungi containing amutation in the mitochondrial cytochrome b gene conferring resistance toQo inhibitors, wherein the mutation is G143A or F129L.

The term “cereals” comprises wheat or barley.

These fungi on wheat or barley containing a mutation in themitochondrial cytochrome b gene conferring resistance to Qo inhibitors,wherein the mutation is G143A or F129L, are hereinafter referred to as“resistant fungi”.

Resistant fungi on wheat or barley in the course of the use of thepresent invention, wherein the mutation is G143A are

Septoria tritici, (leaf blotch) on wheat,

Microduchium nivale, (head blight) on wheat,

Blumeria graminis f sp. tritici, (powdery mildew) on wheat,

Phaesphaeria nodorum, (leaf blotch) on wheat,

Pyrenophora tritici-repentis, (tan spot) on wheat,

Rhynchosporium secalis, (leaf blotch) on barley,

Blumeria graminis f. sp. hordei, (powdery mildew) on barley and

Ramularia collo-cygni, (leaf spot) on barley.

The resistant fungi on wheat or barley in the course of the use of thepresent invention, wherein the mutation is F129L is Pyrenophora teres,(net blotch) on barley, Puccinia recondita (brown or leaf rust) on wheator barley,

Puccinia striiformis (stripe or yellow rust) on wheat or barley,

In soybean, the following pathogens show increasing resistance towardsQo inhibitors due to their G143A mutation:

Cercospora sojina (frogeye leaf spot) and Corynespora cassiicola (targetspot).

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is wheat, andthe resistant fungi is Septoria tritici.

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is wheat, andthe resistant fungi is Microduchium nivale.

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is wheat, andthe resistant fungi is Blumeria graminis f. sp. tritici

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is wheat, andthe resistant fungi is Phaesphaeria nodorum.

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is wheat, andthe resistant fungi is Pyrenophora tritici-repentis.

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is barely, andthe resistant fungi is Rhynchosporium secalis.

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is barely, andthe resistant fungi is Blumeria graminis f. sp. hordei.

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is barely, andthe resistant fungi is Pyrenophora teres.

Thus, the present invention relates to the use of compound I forcombating resistant fungi on cereals, wherein the cereal is barely, andthe resistant fungi is Ramularia collo-cygni.

The term “fruits” comprises apples or grapes.

The fungi on apples or grapes containing a G143A mutation in themitochondrial cytochrome b gene conferring resistance to Qo inhibitorsare hereinafter referred to as “resistant fungi”. Resistant fungi onapples or grapes in the course of the use of the present invention are

Venturia inaequalis (scab) on apple,

Uncinula necator (powdery mildew) on grapes and

Plasmopara viticola (downy mildew) on grapes.

Resistant fungi in the course of the use of the present invention,wherein the mutation is G143A are

Pyricularia oryzae (blast) on rice,

Ustilago maydis (smut) on maize,

Ascochyta rabiei (ascochyta blight) on chickpea,

Didymella rabiei (ascochyta blight) on chickpea,

Cercospora beticola (leaf spot) on sugar beets,

Corynespora cassiicola (target spot) on cucumber,

Didymella bryoniae (gummy stem blight) on cucurbits,

Didymella bryoniae (gummy stem blight) on watermelon,

Podosphera fusca (powdery mildew) on cucumber,

Podosphera xanthii (powdery mildew) on cucurbits,

Pseudoperenospora cubensis (downy mildew) on cucurbits,

Sphaerotheca fuliginea (powdery mildew) on cucumber,

Alternaria alternata (leaf spot) on potato,

Mycovellosiealla nattrassii (leaf mold) on Eggplant,

Stemphylium vesicarium (purple spot) on asparagus,

Alternaria alternata (Alternaria blotch) on apple,

Alternaria malus (Alternaria blotch) on apple,

Alternaria alternata (Alternaria brown spot) on citrus,

Alternaria arborescens (Alternaria Late blight) on pistachio,

Alternaria alternata (Alternaria Late blight) on pistachio,

Alternaria tenuissima (Alternaria Late blight) on pistachio,

Botrytis cinerea (grey mold) on citrus,

Botrytis cinerea (grey mold) on kiwi,

Botrytis cinerea (grey mold) on strawberry,

Colletotrichum gloeosporioides (anthracnose) on strawberry,

Sphaerotheca aphanis var. aphanis (powdery mildew) on strawberry,

Fusicladium carpophlium (leaf spot) on almond,

Mycosphaerella fijiensis (black sigatoka) on banana,

Stemphylium vesicarium (brown spot) on pears,

Colletotrichum graminicola (leaf Spot) on grass, and

Pyricularia grisea (gray leafspot) on grass; and

Monilinia taxa (brown rot) on fruits (including, but not limited to asapple, citrus, kiwi, strawberry, watermelon, banana and pears);

Monilinia fructigena (brown rot) on fruits (including, but not limitedto as apple, citrus, kiwi, strawberry, watermelon, banana and pears);and

Monilinia fijiensis (brown rot) on fruits (including, but not limited toas apple, citrus, kiwi, strawberry, watermelon, banana and pears).

The resistant fungi in the course of the use of the present invention,wherein the mutation is F129L is Rhizoctonia solani (sheet blight) onrice and Alternaria solani (leaf spot) on potato.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isrice and the resistant fungi is Pyricularia oryzae.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isrice and the resistant fungi is Rhizoctonia solani.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ismaize and the resistant fungi is Ustilago maydis.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ischickpea and the resistant fungi is Ascochyta rabiei.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ischickpea and the resistant fungi is Didymella rabiei.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant issugar beets and the resistant fungi is Cercospora beticola.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iscucumber and the resistant fungi is Corynespora cassiicola.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iscucurbits and the resistant fungi is Didymella bryoniae.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iswatermelon and the resistant fungi is Didymella bryoniae.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iscucumber and the resistant fungi is Podosphera fusca.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iscucurbits and the resistant fungi is Podosphera xenthil.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iscucurbits and the resistant fungi is Pseudoperenospora cubensis.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iscucumber and the resistant fungi is Sphaerotheca fuliginea.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ispotato and the resistant fungi is Alternaria solani.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ispotato and the resistant fungi is Alternaria alternata.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iseggplant and the resistant fungi is Mycovellosiealla nattrassil.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isasparagus and the resistant fungi is Stemphylium vestcarium.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isapple and the resistant fungi is Alternaria alternata.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isapple and the resistant fungi is Alternaria malus.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iscitrus and the resistant fungi is Alternaria alternata.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ispistachio and the resistant fungi is Alternaria arborescens.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ispistachio and the resistant fungi is Alternaria alternata.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ispistachio and the resistant fungi is Alternaria tenuissima.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iscitrus and the resistant fungi is Botrytis cinerea.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant iskiwi and the resistant fungi is Botrytis cinerea.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isstrawberry and the resistant fungi is Botrytis cinerea.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isstrawberry and the resistant fungi is Colletotrichum gloeosporioides.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isstrawberry and the resistant fungi is Sphaerotheca alphanis var.aphanis.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isalmond and the resistant fungi is Fusicladium carpophilum.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isbanana and the resistant fungi is Mycosphaerella fijiensis.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant ispears and the resistant fungi is Stemphylium vesicarium.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isgrass and the resistant fungi is Colletotrichum graminicola.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isgrass and the resistant fungi is Pyricuiaria grisea.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isfruits and the resistant fungi is Monilinia taxa.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isfruits and the resistant fungi is Monilinia fructigena.

Thus, the present invention relates to the use of the mixture forcombating resistant fungi on agricultural plants, wherein the plant isfruits and the resistant fungi is Monilinia fijiensis.

The mixtures according to the present invention, respectively, are alsosuitable for controlling harmful fungi in the protection of storedproducts or harvest and in the protection of materials.

The term “protection of materials” is to be understood to denote theprotection of technical and non-living materials, such as adhesives,glues, wood, paper and paperboard, textiles, leather, paint dispersions,plastics, cooling lubricants, fiber or fabrics, against the infestationand destruction by harmful microorganisms, such as fungi and bacteria.As to the protection of wood and other materials, the particularattention is paid to the following harmful fungi: Ascomycetes such asOphiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophomaspp. Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.;Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllumspp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. andTyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporiumspp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomycesspp. and Zygomycetes such as Mucor spp., and in addition in theprotection of stored products and harvest the following yeast fungi areworthy of note: Candida spp. and Saccharomyces cerevisae.

They are particularly important for controlling a multitude of fungi onvarious cultivated plants, such as bananas, cotton, vegetable species(for example cucumbers, beans and cucurbits), cereals such as wheat,rye, barley, rice, oats; grass coffee, potatoes, corn, fruit species,soya, tomatoes, grapevines, ornamental plants, sugar cane and also on alarge number of seeds. In a preferred embodiment, the inventive mixturesare used in soya (soybean), cereals and corn.

In general, “pesticidally effective amount” means the amount of theinventive mixtures or of compositions comprising the mixtures needed toachieve an observable effect on growth, including the effects ofnecrosis, death, retardation, prevention, and removal, destruction, orotherwise diminishing the occurrence and activity of the targetorganism. The pesticidally effective amount can vary for the variousmixtures/compositions used in the invention. A pesticidally effectiveamount of the mixtures/compositions will also vary according to theprevailing conditions such as desired pesticidal effect and duration,weather, target species, locus, mode of application, and the like.

As said above, the present invention comprises a method for improvingthe health of plants, wherein the plant, the locus where the plant isgrowing or is expected to grow or plant propagation material, from whichthe plant grows, is treated with an plant health effective amount of aninventive mixture.

The term “plant effective amount” denotes an amount of the inventivemixtures, which is sufficient for achieving plant health effects asdefined herein below. More exemplary information about amounts, ways ofapplication and suitable ratios to be used is given below. Anyway, theskilled artisan is well aware of the fact that such an amount can varyin a broad range and is dependent on various factors, e.g. the treatedcultivated plant or material and the climatic conditions.

When preparing the mixtures, it is preferred to employ the pure activecompounds, to which further active compounds against pests, such asinsecticides, herbicides, fungicides or else herbicidal orgrowth-regulating active compounds or fertilizers can be added asfurther active components according to need.

The inventive mixtures are employed by treating the fungi or the plants,plant propagation materials (preferably seeds), materials or soil to beprotected from fungal attack with a pesticidally effective amount of theactive compounds. The application can be carried out both before andafter the infection of the materials, plants or plant propagationmaterials (preferably seeds) by the pests.

In the context of the present invention, the term plant refers to anentire plant, a part of the plant or the propagation material of theplant.

The inventive mixtures and compositions thereof are particularlyimportant in the control of a multitude of phytopathogenic fungi onvarious cultivated plants, such as cereals, e. g. wheat, rye, barley,triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits,such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums,peaches, almonds, cherries, strawberries, raspberries, blackberries orgooseberries; leguminous plants, such as lentils, peas, alfalfa orsoybeans; oil plants, such as rape, mustard, olives, sunflowers,coconut, cocoa beans, castor oil plants, oil palms, ground nuts orsoybeans; cucurbits, such as squashes, cucumber or melons; fiber plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits orpaprika; lauraceous plants, such as avocados, cinnamon or camphor;energy and raw material plants, such as corn, soybean, rape, sugar caneor oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines(tablegrapes and grape juice grape vines); hop; turf; sweet leaf (alsocalled Stevia); natural rubber plants or ornamental and forestry plants,such as flowers, shrubs, broad-leaved trees or evergreens, e. g.conifers; and on the plant propagation material, such as seeds, and thecrop material of these plants.

Preferably, the inventive mixtures and compositions thereof,respectively are used for controlling a multitude of fungi on fieldcrops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats,rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugarcane; fruits; vines; ornamentals; or vegetables, such as cucumbers,tomatoes, beans or squashes.

Preferably, treatment of plant propagation materials with the inventivemixtures and compositions thereof, respectively, is used for controllinga multitude of fungi on cereals, such as wheat, rye, barley and oats;potatoes, tomatoes, vines, rice, corn, cotton and soybeans.

Most preferably are use of the inventive mixtures for the combinations1-1 to 1-20 as disclosed in Table 1:

Use Component 1 Component 2 Crop Pathogen 1-1 compound I compound IIwheat Erysiphe graminis tritici 1-2 compound I compound II wheatPyrenophora tritici- repentis 1-3 compound I compound II wheat Fusariumgraminea- rum 1-4 compound I compound II wheat Zymoseptoria tritici 1-5compound I compound II wheat Puccime graminis tritici 1-6 compound Icompound II wheat Puccime triticina 1-7 compound I compound II wheatPuccinia striiformis 1-8 compound I compound II wheat Rhynchosporium se-callis 1-9 compound I compound II wheat Rhizoctonia cerealis 1-10compound I compound II wheat Puccime recondita 1-11 compound I compoundII barley Erysiphe graminis 1-12 compound I compound II barleyDrechslera teres 1-13 compound I compound II barley Mycosphaerella gra-minicola 1-14 compound I compound II barley Puccinia triticina 1-15compound I compound II barley Puccinia striiformis 1-16 compound Icompound II barley Rhynchosporium se- calis 1-17 compound I compound IIbarley Rhizoctonia cerealis 1-18 compound I compound II barley Pucciniarecondita 1-19 compound I compound II maize Bipolaris zeicola 1-20compound I compound II maize Cercospora zeae- maydis 1-21 compound Icompound II maize Phaeosphaeria maydis 1-22 compound I compound II maizePuccinia polysora

The term “cultivated plants” is to be understood as including plantswhich have been modified by breeding, mutagenesis or genetic engineeringincluding but not limiting to agricultural biotech products on themarket or in development (cf. http://cera-gmc.org/, see GM crop databasetherein). Genetically modified plants are plants, which genetic materialhas been so modified by the use of recombinant DNA techniques that undernatural circumstances cannot readily be obtained by cross breeding,mutations or natural recombination. Typically, one or more genes havebeen integrated into the genetic material of a genetically modifiedplant in order to improve certain properties of the plant. Such geneticmodifications also include but are not limited to targetedpost-translational modification of protein(s), oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylatedor farnesylated moieties or PEG moieties.

Plants that have been modified by breeding, mutagenesis or geneticengineering, e. g. have been rendered tolerant to applications ofspecific classes of herbicides, such as auxin herbicides such as dicambaor 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxygenase(HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactatesynthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones;enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such asglyphosate; glutamine synthetase (GS) inhibitors such as glufosinate;protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitorssuch as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e.bromoxynil or ioxynil) herbicides as a result of conventional methods ofbreeding or genetic engineering. Furthermore, plants have been maderesistant to multiple classes of herbicides through multiple geneticmodifications, such as resistance to both glyphosate and glufosinate orto both glyphosate and a herbicide from another class such as ALSinhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors.These herbicide resistance technologies are e. g. described in PestManagement Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005,269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009,108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1185;and references quoted therein. Several cultivated plants have beenrendered tolerant to herbicides by conventional methods of breeding(mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany)being tolerant to imidazolinones, e. g. imazamox, or ExpressSun®sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g.tribenuron. Genetic engineering methods have been used to rendercultivated plants such as soybean, cotton, corn, beets and rape,tolerant to herbicides such as glyphosate and glufosinate, some of whichare commercially available under the trade names RoundupReady®(glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® (imidazolinonetolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant,Bayer CropScience, Germany).

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more insecticidal proteins,especially those known from the bacterial genus Bacillus, particularlyfrom Bacillus thuringiensis, such as δ-endotoxins, e. g. CryIA(b),CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c;vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A;insecticidal proteins of bacteria colonizing nematodes, e. g.Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, suchas scorpion toxins, arachnid toxins, wasp toxins, or otherinsect-specific neurotoxins; toxins produced by fungi, suchStreptomycetes toxins, plant lectins, such as pea or barley lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin or papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ionchannel blockers, such as blockers of sodium or calcium channels;juvenile hormone esterase; diuretic hormone receptors (helicokininreceptors); stilben synthase, bibenzyl synthase, chitinases orglucanases. In the context of the present invention these insecticidalproteins or toxins are to be understood expressly also as pre-toxins,hybrid proteins, truncated or otherwise modified proteins. Hybridproteins are characterized by a new combination of protein domains,(see, e. g. WO 02/015701). Further examples of such toxins orgenetically modified plants capable of synthesizing such toxins aredisclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427529, EP-A 451 878, WO 03/18810 and WO 03/52073. The methods forproducing such genetically modified plants are generally known to theperson skilled in the art and are described, e. g. in the publicationsmentioned above. These insecticidal proteins contained in thegenetically modified plants impart to the plants producing theseproteins tolerance to harmful pests from all taxonomic groups ofathropods, especially to beetles (Coeloptera), two-winged insects(Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).Genetically modified plants capable to synthesize one or moreinsecticidal proteins are, e. g., described in the publicationsmentioned above, and some of which are commercially available such asYieldGard® (corn cultivars producing the Cry1Ab toxin), YieldGard® Plus(corn cultivars producing Cry1Ab and Cry3Bb1 toxins), Starlink® (corncultivars producing the Cry9c toxin), Herculex® RW (corn cultivarsproducing Cry34Ab1, Cry35Ab1 and the enzymePhosphinothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cottoncultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivarsproducing the Cry1Ac toxin), Bollgard® II (cotton cultivars producingCry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing aVIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin);Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e. g.Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivarsproducing the Cry1Ab toxin and PAT enzyme), MIR604 from Syngenta SeedsSAS, France (corn cultivars producing a modified version of the Cry3Atoxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium(corn cultivars producing the Cry3Bb1 toxin), IPC 531 from MonsantoEurope S.A., Belgium (cotton cultivars producing a modified version ofthe Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium(corn cultivars producing the Cry1F toxin and PAT enzyme).

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more proteins to increasethe resistance or tolerance of those plants to bacterial, viral orfungal pathogens. Examples of such proteins are the so-called“pathogenesis-related proteins” (PR proteins, see, e. g. EP-A 392 225),plant disease resistance genes (e. g. potato cultivars, which expressresistance genes acting against Phytophthora infestans derived from themexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potatocultivars capable of synthesizing these proteins with increasedresistance against bacteria such as Erwinia amylvora). The methods forproducing such genetically modified plants are generally known to theperson skilled in the art and are described, e. g. in the publicationsmentioned above.

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more proteins to increasethe productivity (e. g. bio mass production, grain yield, starchcontent, oil content or protein content), tolerance to drought, salinityor other growth-limiting environmental factors or tolerance to pests andfungal, bacterial or viral pathogens of those plants.

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of substances of content ornew substances of content, specifically to improve human or animalnutrition, e. g. oil crops that produce health-promoting long-chainomega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera®rape, DOW Agro Sciences, Canada).

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of substances of content ornew substances of content, specifically to improve raw materialproduction, e. g. potatoes that produce increased amounts of amylopectin(e. g. Amflora® potato, BASF SE, Germany).

The separate or joint application of the compounds of the inventivemixtures is carried out by spraying or dusting the seeds, the seedlings,the plants or the soils before or after sowing of the plants or beforeor after emergence of the plants.

The inventive mixtures and the compositions comprising them can be usedfor protecting wooden materials such as trees, board fences, sleepers,etc. and buildings such as houses, outhouses, factories, but alsoconstruction materials, furniture, leathers, fibers, vinyl articles,electric wires and cables etc. from ants and/or termites, and forcontrolling ants and termites from doing harm to crops or human being(e.g. when the pests invade into houses and public facilities).

Customary application rates in the protection of materials are, forexample, from 0.01 g to 1000 g of active compound per m² treatedmaterial, desirably from 0.1 g to 50 g per m².

For use in spray compositions, the content of the mixture of the activeingredients is from 0.001 to 80 weight %, preferably from 0.01 to 50weight % and most preferably from 0.01 to 15 weight %.

Microtest

The active compounds were formulated separately as a stock solutionhaving a concentration of 10000 ppm in dimethyl sulfoxide.

EXAMPLE 1 Activity Against Early Blight Caused by Altemana solani

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Alternaria solani in an aqueousbiomalt or yeast-bactopeptone-glycerine or DOB solution was then added.The plates were placed in a water vapor-saturated chamber at atemperature of 18° C. Using an absorption photometer, the MTPs weremeasured at 405 nm 7 days after the inoculation.

Calculated Active efficacy compound/ Concentra- according active tionObserved to Colby Synergism mixture (ppm) Mixture efficacy (%) (%)Compound I 4 — 30 1 —  8 0.25 —  7 Compound II 0.016 — 11 Compound I 4250 : 1 71 38 33 Compound II 0.016

The measured parameters were compared to the growth of the activecompound-free control variant (100%) and the fungus-free and activecompound-free blank value to determine the relative growth in % of thepathogens in the respective active compounds.

These percentages were converted into efficacies.

An efficacy of 0 means that the growth level of the pathogenscorresponds to that of the untreated control; an efficacy of 100 meansthat the pathogens were not growing.

The expected efficacies of active compound mixtures were determinedusing Colby's formula [R. S. Colby, “Calculating synergistic andantagonistic responses of herbicide combinations”, Weeds 15, 20-22(1967)] and compared with the observed efficacies.

1. A fungicidal mixture comprising, as active components, 1)4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1yl)propyl]-3-pyridyl]oxy]benzonitrileas compound I and 2)1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one as compound II.
 2. The mixture as claimed in claim 1,wherein ratio by weight of compound I and compound II is from 100:1 to1:100.
 3. A pesticidal composition, comprising a liquid or solid carrierand a mixture as defined in any of claim
 1. 4. (canceled)
 5. The methodas defined in claim 11 for controlling phytopathogenic harmful fungi oncereals.
 6. The method as defined in claim 11 for controllingphytopathogenic harmful fungi on corn.
 7. The method as defined in claim11 for controlling phytopathogenic harmful fungi wherein the fungicontains a mutation in the mitochondrial cytochrome b gene conferringresistance to Qo inhibitors, wherein the mutation is G143A or F129L. 8.The method as defined in claim 5 against Blumeria (formerly Erysiphe)graminis on cereals; Drechslera (syn. Helminthosporium, teleomorph:Pyrenophora) spp. on cereals; Fusarium (teleomorph: Gibberella) spp.;Mycosphaerella spp. on cereals; Puccinia spp. (rusts) on cereals;Rhynchosporium secalis and R. commune (scald) on cereals; Septoria spp.on cereals.
 9. The method as defined in claim 6 against Bipolaris andDrechslera spp. (teleomorph: Cochliobolus spp.); Cercospora spp.(Cercospora leaf spots) on corn. Phaeosphaeria maydis and Pucciniapolysora on corn.
 10. The method as defined in claim 6 againstCercospora spp. (Cercospora leaf spots) sugar beets.
 11. A method forcontrolling phytopathogenic pests, wherein the pest, their habitat,breeding grounds, their locus or the plants to be protected against pestattack, the soil or plant propagation material are treated with aneffective amount of the mixture as defined in claim
 1. 12. The method asclaimed in claim 11, wherein the mixture is applied in an amount of from0.01 g to 10 kg per 100 kg of plant propagation materials.
 13. Themethod as claimed in claim 11, wherein the mixture is appliedsimultaneously, jointly or separately, or in succession.